title: Efficient decomposition of perfluorocarboxylic acids and alternative fluorochemical surfactants in hot water.
abstract: Decomposition of C5-C9 perfluorocarboxylic acids (PFCAs) and perfluoroether carboxylic acids (alternatives to PFCA-based surfactants) in hot water in a sealed reactor was investigated. Although PFCAs showed almost no decomposition in hot water at 80 degrees C in the absence of persulfate (S2O8(2-)), the addition of S2O8(2-) to the reaction system led to efficient decomposition, even at this relatively low temperature. The major products in the aqueous and gas phases were F- ions and CO2, respectively, and short-chain PFCAs were also detected in the aqueous phase. For example, when an aqueous solution containing perfluorooctanoic acid (PFOA, 374 microM) and S2O8(2-) (50.0 mM) was heated at 80 degrees C for 6 h, PFOA concentration in the aqueous phase fell below 1.52 microM (detection limit of HPLC with conductometric detection), and the yields of F- ions [i.e., (moles of F- formed) /(moles of fluorine content in initial PFOA)] and CO2 [i.e, (moles of CO2 formed) /(moles of carbon content in initial PFOA)] were 77.5% and 70.2%, respectively. This method was also effective in decomposing perfluoroether carboxylic acids, such as CF3OC2F4OCF2COOH, CF3OC2F4OC2F4OCF2COOH, and C2F5OC2F4OCF2COOH, which are alternatives to PFCA-based surfactants, producing F- and CO2 with yields of 82.9-88.9% and 87.7-100%, respectively, after reactions at 80 degrees C for 6 h. In addition, the method was successfully used to decompose perfluorononanoic acid in a floor wax solution. When PFOAwastreated at a higher temperature (150 degrees C), other decomposition reactions occurred: the formation of F- and CO2 was dramatically decreased, and 1H-perfluoroalkanes (C(n)F(2n+1)H, n = 4-7) formed in large amounts. This result clearly indicates that treatment with high-temperature water was not suitable for the decomposition of PFCAs to F-: surprisingly, the relatively low temperature of 80 degrees C was preferable.
authors.affiliation: National Institute of Advanced Industrial Science and Technology (AIST), AIST Tsukuba West, 16-1 Onogawa, Tsukuba 305-8569, Japan. h-hori@aist.go.jp
authors.forename: Hisao
authors.initials: H
authors.lastname: Hori
authors.forename: Yumiko
authors.initials: Y
authors.lastname: Nagaoka
authors.forename: Misako
authors.initials: M
authors.lastname: Murayama
authors.forename: Shuzo
authors.initials: S
authors.lastname: Kutsuna
mesh_terms: D002264:Carboxylic Acids / Q000737:chemistry*; D005466:Fluorocarbons / Q000737:chemistry*; D006358:Hot Temperature; D007700:Kinetics; D012996:Solutions; D013447:Sulfites / Q000737:chemistry; D013501:Surface-Active Agents / Q000737:chemistry*; D013997:Time Factors; D014867:Water / Q000737:chemistry*; D014885:Waxes / Q000737:chemistry
chemical_list: D002264:Carboxylic Acids; D005466:Fluorocarbons; D012996:Solutions; D013447:Sulfites; D013501:Surface-Active Agents; D014885:Waxes; D014867:Water